Optical colored glasses

ABSTRACT

The invention concerns an optical colored glass of the composition (in % in weight on oxide basis) SiO 2  50-62; K 2 O 10-25; Na 2 O 0-14; Al 2 O 3  0-2; B 2 O 3  3-5; ZnO 13.5-37; F 0-1; TiO 2  0-7; In 2 O 3 0-2; Ga 2 O 3  0-2; SO 3 0-1; SeO 2 0-1; C 0-1; M I M III Y 2   II  0.1-3, whereby M I =Cu+ and/or Ag+ and/or M III =In 3 + and/or Ga 3+  and/or Al 3+  and/or Y II ═S 2−  and/or Se 2−  and at least 0.1% in weight of the oxide (M 2 O 3 ) of the M III , which is/are present in M I M III Y II   2 , and with at least 0.2% in weight of the oxide, of the Y II , which is/are present in M I M III Y II   2 .

[0001] The subject of the invention is an optical colored glass, its use as optical square edge filter as well as an optical square edge filter.

[0002] The subject of the invention is also a procedure for the production of optical colored glasses.

[0003] Optical square edge filters are characterized by characteristic transmission properties. Thus ones with long pass characteristic show a low transmission in the short-wave range, which rises over a narrow spectral region to high transmission and remains high in the long-wave range. The range of low transmission (pure transmission value τ_(IS)≦10⁻⁵) is called stop band, the range of high transmission (pure transmission value τ_(ip)>0.99) as pass range or pass band.

[0004] Optical square edge filters are characterized by means of certain parameters. Thus the absorption edge of such a filter is usually indicated as the so-called edge wavelength λC. It corresponds to the wavelength, for which the spectral pure transmission factor between stop band and pass band amounts to half of the maximum value.

[0005] Optical square edge filters are usually realized by colored glasses, in which through colloidal elimination of semiconductor compounds during the cooling of the molten mass or through additional thermal treatment the coloring is produced. One speaks of so-called tarnish glasses.

[0006] Commercial square edge filters are manufactured by doping the basic glasses with cadmium semiconductor compounds. Depending upon the edge position CdS, CdSe, CdTe or also mixed compounds of these semiconductors are used for this. With these square edge filters edge wavelengths of a maximum of 850 nm can be reached. In addition, for the use e.g. in IR cameras or as laser protecting glass longer-wave square edges are desired. Due to the toxic and the carcinogenic characteristics of cadmium it is desired to be able to do without these compounds and to use other doping factors instead. In order to achieve equal or similar absorption properties of the glasses, alternative doping factors must likewise consist of semiconductors with direct optical transitions, because only through the special band structure of the semiconductors, the energy gap between valence band and conduction band, the sharp transitions between absorption range and transmission range of the glasses and thus to the filter characteristics of these glasses take place.

[0007] The I-III-VI semiconductor system, e.g. copper-indium-bisulfide and copper-indium-biselenide could also represent an alternative to the CdS—, CdSe—, CdTe— compounds. These for a long time well-known semiconductors are so far only of greater practical importance in the photovoltaic.

[0008] In a number of Russian and Soviet patent applications for a very close glass composition range are already CuInS₂ doped and/or CuInS₂—CuInSe₂ mix doped glasses described, which are supposed to be applied as filters: SU 167702A1, SU 1527199A1, RU 2073657C1, SU 1770297A1, SU 1770298A1, SU 1678786A1, SU 1701658A1, SU 1677025, SU 1675239A1, SU 1675240A1 and SU 1787963A1. All these glasses have in common that they contain no or very little B₂O₃ and no or very little ZnO and that they have with portions of up to 79% in weight a high SiO₂ content. The glasses of these applications do not possess good chemical stabilities.

[0009] It is subject of the invention to make chemically resistant optical Cd-free colored glasses available, which possess square edge characteristics and exhibit absorption edges between >0.4 μm and 1.2 μm.

[0010] It is further a subject of the invention to make such square edge filters available.

[0011] It is further a subject of the invention to make a procedure available for the production of optical colored glasses.

[0012] The tasks are solved through a glass according to claim 1, a procedure according to claim 9, a usage according to claim 10 and a square edge filter according to claim 11.

[0013] Alkali-zinc-silicate-glass serves as basic glass. The basic glass is based on the oxides SiO₂, which have the function of forming the structure, ZnO, which has the function of forming the structure and transforming the structure, and K₂O and optional Na₂O, which have the function of transforming the structure.

[0014] SiO₂ constitutes the main part of the glass with 50 to 62% in weight. Higher portions would increase the crystallization tendency and would worsen the fusibility.

[0015] ZnO is present with 13.5 to 37% in weight. It increases the resistance to thermal shock of the glass, a characteristic, which is substantial for the intended use of the glass behind or in front of strong radiation sources, which are always accompanied by a high temperature emission. ZnO supports in addition the homogeneous nano-crystallization of the doping material in the glass. I.e. during the warming up of the glass in such a way homogeneous crystal growth of the semiconductor doping factors is ensured. The very pure and bright color and the sharp absorption edge of the glasses result from these mono dispersive crystallites. With ZnO contents lower than 13.5% in weight the glasses show a worse or no tarnish behavior. A ZnO portion of at least 18% in weight is preferred. The mentioned upper limit of ZnO is meaningful, since glasses, which exhibit a higher ZnO content, have a tendency for the formation of drip-like elimination areas and thus for separation. The separation tendency of such “Zinc-silicate glasses” can be lowered by the use of the structure transformer K₂O. In order to prevent micro elimination of ZnO enriched areas and to reduce their processing temperature, the glasses contain 10 to 25% in weight, preferably 18 to 25% in weight K₂O. The glass can contain in addition up to 14% in weight Na₂O, which affects mainly the physical characteristics like the fixed viscosity reference points and the coefficients of expansion. With higher concentration of Na₂O the chemical stability would decrease, the coefficient of expansion would be too high and the transformation temperature would be too low. Preferably the sum of amounts of K₂O and Na₂O are 29% in weight at the most. The other expensive alkali oxides Li₂O, Rb₂O, Cs₂O can in principle also be used, however due to their price disadvantage they are preferably are not used.

[0016] Besides ZnO also B₂O₃ promotes the resistance to thermal shock of the glass. B₂O₃ is contained with 3 to 5% in weight in the glass. B₂O₃ improves the fusibility of the glass.

[0017] The glass can contain further up to 1% in weight F. F serves for the improvement of the fusibility, i.e. it lowers the viscosity of the glass.

[0018] The glass can contain also up to 1% in weight C. C serves as reducing agent, in order to prevent an oxidation of the compound semiconductors.

[0019] The glass is suitable in an outstanding fashion for the formation of nano-crystals from compound semiconductors of the class I-III-VI which is distributed colloidal in the glass.

[0020] The nano-crystallization is affected during the tarnish process by the glass viscosity, the oversaturation, the solubility product and the growth rate of the color carriers. The tarnish process, which contains the coloring and thus the elimination of the crystallites of the semiconductor compounds, takes place either already at the cooling of the glasses and/or through a further temperature treatment within the range Tg<200K. The tarnish temperature and tarnish times thereby affect the crystallite size. The larger the crystallites become, the smaller becomes the band gap of the semiconductors and the more longer-waved (=red) is the inherent color of the glass. The specialist knows how to control these factors if possible.

[0021] The glasses contain the compound semiconductors M^(I)M^(III)Y^(II) ₂ (whereby M^(I)=Cu⁺, Ag⁺, M^(III)=In³⁺, Ga³⁺, Al³⁺, Y^(II)═S²⁻, Se²⁻ can be) as chromophore components, thus as doping factors to impart the filter characteristics,.

[0022] The sum of the compound semiconductors in the glass amounts to at least 0.1% in weight, which corresponds to the minimum concentration of colloidal micro crystals distributed in the glass for the light absorption, and at the most 3% in weight, preferably at the most 1% in weight. Higher contents than 3% in weight would lower the transmission within the pass range after the tarnish process in an unacceptable manner. From the mentioned ternary semiconductor systems M^(I)M^(III)Y^(II) ₂ are all edge components, thus e.g. CuInS₂, CuInSe₂, CuGaS₂, CuGaSe₂, AgInS₂, AgInSe₂, AgGaS₂ and AgGaSe₂ as well as all mixed compounds of two component systems or multi component systems usable. It is also possible to use two or several edge components at the same time.

[0023] Doping factors of one or several components from the system CuIn(Se_(1−x)S_(x))₂ with x=0 to 1, i.e. of the edge components CuInSe₂ and CuInS₂ as well as by their mixed compounds are particularly preferable. Particularly preferable is a doping factor content from 0.1 to 0.5% in weight.

[0024] The absorption edge in the area between 360 nm to 1200 nm can be shifted by variations of the portions of the respective compounds and the conditions of the tarnish process. With doping factor contents between 0.1 and 0.5% in weight, in particular CuIn(Se_(1x)S_(x))₂ edge lengths between 400 nm and 1200 nm can be achieved.

[0025] For the characteristics as tarnish gas the components In₂O₃ and Ga₂O₃ with contents of 0-2% in weight in each case as well as SO₃ and SeO₂ with contents of 0-1% in weight are very favorable. These components prevent possible evaporations of the components In₂O₃, Ga₂O₃, S and Se from the compound semiconductors. Thus the chalcopyrite remains as the chromophore component in or close to the intended stoichiometry and thus at the desired specific edge position. Therefore the glasses contain at least 0.1% in weight of the oxide of the M^(III), thus M₂O₃, which is/are present in M^(I)M^(III)Y^(II) ₂, and at least 0.2% in weight of the oxide of Y^(II), which is/are present in M^(I)M^(III)Y^(II) ₂.

[0026] It is particularly preferable, to use SO₃ and/or SeO₂ not with elemental S and/or Se but in the form of ZnS and/or ZnSe. Preferable 0.1-4% in weight ZnS and/or ZnSe are used. Both components promote the structure of the chromophore crystals of the semiconductor compounds such as CuInS₂ and CuInSe₂ as auxiliary crystal components and thus the edge steepness and the transmission in the pass range.

[0027] With this procedure for the production of optical colored glasses of the composition range (in % in weight on oxide basis) SiO₂ 50-62, K₂O 10-25; Na₂O 0-14; MgO 0-4; CaO 0-10, BaO 0-10, SrO 0-10; P₂O₅ 0-10; Al₂O₃ 0-2; B₂O₃ 3-5; ZnO 13.5-37; F 0-1, TiO₂ 0-7; In₂O₃ 0-2; Ga₂O₃ 0-2; SO₃ 0-1; SeO₂ 0-1; C 0-1; and the doping factor M^(I)M^(III)Y^(II) ₂ with M^(I)=Cu⁺, Ag⁺, M^(III)=In³⁺, Ga³⁺, Al³⁺, Y″═S²⁻, Se²⁻ with at least 0.1% in weight of the oxide (M₂O₃) of the M^(III), which is/are present in M^(I)M^(III)Y^(II) ₂, and with at least 0.2% in weight of the oxide, or Y″, which is/are present in M^(I)M^(III)Y^(II) ₂, with the process steps glass batch preparation, melting of the glass, cooling and warming up, with which 0.1-4% in weight ZnS and/or ZnSe are added to the glass batch, tarnish glasses with defined edge length can be manufactured easily, purposeful and reproducible. The requirements of the to be met conditions regarding temperature and time of the process steps cooling and warming up are smaller than with conventional procedures. The term melting here combines the steps refining, homogenizing and conditioning for further processing, which follow the melting itself.

[0028] In addition the glass can contain up to 4% in weight MgO, up to 10% in weight CaO, up to 10% in weight BaO, up to 10% in weight SrO, up to 10% in weight P₂O₅, up to 2% in weight Al₂O₃ and up to 7% in weight TiO₂. Al₂O₃ improves the crystallization ability of the glass, MgO and CaO function in the basic glass similar to ZnO. They improve the chemical stability, and they are less expensive than ZnO. BaO and SrO serve for the fine tuning of the coefficient of expansion, transformation temperature and processing temperature. However, since BaO and SrO are more expensive than MgO and SrO, which are similar in many properties, they are preferably not used.

[0029] P205 can partially be exchanged against SiO2 or B2O3 as structure formers. It is useful for the lowering of the viscosity at certain temperatures. P2O5 reduces however the chemical resistance and is therefore preferably not used.

[0030] The component TiO2 in this glass system takes over mainly the function of the supporting UV-blocking. Square edge filters must fulfill an optical density in the stop band. Additional UV absorbers such as TiO2 can support this.

[0031] The glasses can be molten with the help of the well-known usual melting procedures for tarnish glasses, i.e. under neutral and/or reducing conditions at temperatures of approx. 1100-1550° C. The glasses build already during the cooling process and/or through an additional temperature treatment finely divided nano-crystallites, which cause the color and/or a tarnishing of the glass.

[0032] For the improvement of the glass quality, one or more well-known refining media in the usual quantities can be added to the glass batch for the refining of the glass. Thus the glass exhibits a particularly good internal glass quality regarding the non-existence of bubbles and streaks.

EXAMPLES

[0033] Six examples of glasses according to the invention were molten from the usual optical raw materials. The raw materials were weighed, afterwards mixed thoroughly, melted in usual procedures with approx. 1300° C. to 1550° C. and well homogenized. The temperature at pouring was approx. 1450° C.

[0034] In Table 2 the following are indicated: the respective composition (in % in weight) and the edge wavelength λ_(C) [nm] (sample thickness d=3 mm), tarnish temperatures [° C.] and rise times [h].

[0035] Table 1 shows a melting example, for the glass in accordance with example 1 from Table 2. The glass was cooled with 20 K/h and afterwards temperature treated for 3 h at approx. 560° C. The glass possesses an edge wavelength λ_(C) of 420 nm. TABLE 1 Melting example of a 0.5-1-glass batch Originally weighted-in Component % in weight Raw material quantity [g] SiO₂ 52.84 SiO₂ 524.67 B₂O₃ 4.07 B₂O₃ 40.80 ZnO 19.71 ZnO 194.96 K₂O 22.84 K₂CO₃ 332.91 SO₃ 0.1 ZnS 1.02 CuInSe₂ 0.23 CuInSe₂ 2.55

[0036] TABLE 2 Glass composition (in % in weight), edge wavelength λ_(c), tarnish temperature [° C.] and tarnish time [h] (the difference to 100% results from taking into account CuInS₂/CuInSe₂ as CuO, In₂O₃, SO₃/SeO₂) 1 2 3 4 5 6 SiO₂ 52.84 52.9 52.5 52 61.95 52.75 B₂O₃ 4.07 4.07 4.05 4 3 4.05 ZnO 19.71 19.74 19.64 19.4 13.99 19.68 Na₂O — — — — 8.99 — K₂O 22.84 22.86 22.75 22.47 11.59 22.8 SO₃ 0.1 0.16 — — 0.21 — CuInS₂ — 0.22 — 1 0.22 0.091 CuInSe₂ 0.23 — 0.5 — — 0.094 C — — — — 0.05 — λ_(c) [nm] d = 3 mm, 420 324 507 1010 780 416 (tarnish temperature (560/3) (−/0) (−/0) (−/0) (−/0) (−/0) [° C.]/ tarnish time [h]) λ_(c) [nm] d = 3 mm, 460 415 613 1030 898 — (tarnish temperature (560/57) (500/150) (560/57) (590/150) (595/50) [° C.]/ tarnish time [h]) λ_(c) [nm] d = 3 mm, — 521 — — 960 — (tarnish temperature (515/150) (610/150) [° C.]/ tarnish time [h])

[0037] The glasses according to the invention and the glasses manufactured in the procedure according to the invention are especially suitable for the use as optical square edge filters with long pass characteristic due to their transmission course. They show in the stop band a good optical density of ≧3, whereby the optical density is defined as OD (λ)=1 g (1/τ(λ)). Their transmission in approximately the pass band, which is longer-waved compared to the stop band, is sufficiently high with ≧88%. Their absorption edge is sufficiently steep. It can be moved with M^(I)M^(III)Y^(II) doped glasses, for which is M^(I)=Cu⁺, Ag⁺, M^(III)=In³⁺, Ga³⁺, Y^(II)═S²⁻, Se²⁻ between 400 nm and 1200 nm. Therefore the glasses cover with the area of edge position of the usual Cd-containing tarnish glasses as far as possible and go in the long-wave are far beyond these.

[0038] If the glasses contain aluminum doping factors, thus M^(I)-Al (S, Se) compound semiconductors like e.g. CuAlS₂ and CuAlSe₂ or their mixed components alone or in combination with the other mentioned M′M″Y″ systems, then edge lengths up to a minimum of 360 nm are produced.

[0039] When using exclusively the M^(I)-Al—(S, Se) doping factors, preferably the Cu—Al—(S,Se) doping factor, edge lengths between 460 nm and 360 nm is produced preferably between 0.1 and 0.5% in weight.

[0040]FIG. 1 shows the transmissions course (transmission factor versus wave length λ) at samples of the thickness 3 mm of the examples 1 and 2 (reference numbers 2 and 3) as well as a comparison example (reference number 1). The comparison example is the commercially available Cd-containing glass GG 420 of the applicant.

[0041] The glasses according to the invention are environmental friendly, as they do not need any Cd-containing components. Due to their composition they can be easily melted, they are chemically resistant and resistant to thermal shock.

[0042] Their tarnish behavior is easily controllable. This applies in particular to the glasses manufactured in the procedure according to the invention, which exhibit steep absorption edges. 

1. Optical colored glass characterized by a composition (in % in weight) of SiO₂ 50-62 K₂O 10-25 Na₂O  0-14 Al₂O₃ 0-2 B₂O₃ 3-5 ZnO 13.5-37   F 0-1 TiO₂ 0-7 In₂O₃ 0-2 Ga₂O₃ 0-2 SO₃ 0-1 SeO₂ 0-1 C 0-1 M^(I)M^(III)Y^(II) ₂ 0.1-3  

whereby M^(I)=Cu⁺ and/or Ag⁺ M^(III)=In³⁺ and/or Ga³⁺ and/or Al³⁺, Y^(II)═S²⁻ and/or Se²⁻ with at least 0.1% in weight of the oxide (M₂O₃) of the M^(III) which is/are present in M^(I)M^(III)Y^(II) ₂, and with at least 0.2% in weight of the oxide, of Y^(II), which is/are present in M^(I)M^(III)Y^(II) ₂, as well as usual refining media if necessary in usual quantities:
 2. Optical colored glass according to claim 1, characterized by a composition (in % in weight) of SiO₂ 50-62 K₂O 18-25 Na₂O  0-14 B₂O₃ 3-5 ZnO 13.5-37   F 0-1 Al₂O₃ 0-2 TiO₂ 0-7 In₂O₃ 0-2 Ga₂O₃ 0-2 SO₃ 0-1 SeO₂ 0-1 C 0-1

M^(I)M^(III)Y^(II), whereby M^(I)=0.1-1 Cu⁺ and/or Ag⁺, M^(III)= In³⁺ and/or Ga³⁺, Y^(II) ₂ =S²⁻ and/or Se²⁻ with at least 0.1% in weight of the oxide (M₂O₃) of the M^(III) which is/are present in M^(I)M^(III)Y^(II) ₂, and with at least 0.2% in weight of the oxide, of Y^(II), which is/are present in M^(I)M^(III)Y^(II) ₂, as well as usual refining media if necessary in usual quantities.
 3. Optical colored glass, thus characterized that it additionally contains (in % in weight on oxide basis) MgO 0-4  CaO 0-10 BaO 0-10 SrO 0-10 P₂O₅ 0-10

as well as usual refining media if necessary in usual quantities
 4. Optical colored glass according to claim 3, characterized by the fact that it contains between 0.1 and 0.5% in weight CuIn(Se_(1−x)S_(x))₂.
 5. Optical colored glass according to claim 4 with an edge wavelength λC between 360 nm and 1200 nm.
 6. Optical colored glass according to claim 2 with an edge wavelength λC between 400 nm and 1200 nm.
 7. Optical colored glass according to claim 1, characterized by the fact that it contains between 0.1 and 0.5% in weight CuAl (Se_(1−x)S_(x))₂.
 8. Optical colored glass according to claim 7 with an edge wavelength λC between 360 nm and 460 nm.
 9. Procedure for the production of optical colored glasses of the composition range SiO₂ 50-62 K₂O 10-25 Na₂O  0-14 MgO 0-4 CaO  0-10 BaO  0-10 SrO  0-10 P₂O₅  0-10 Al₂O₃ 0-2 B₂O₃ 3-5 ZnO 13.5-37   F 0-1 TiO₂ 0-7 In₂O₃ 0-2 Ga₂O₃ 0-2 SO₃ 0-1 SeO₂ 0-1 C 0-1

M^(I)M^(III)Y^(II) ₂ 0.1-1 whereby M^(I)=Cu⁺, Ag⁺ M^(III)=In³⁺, Ga³⁺, Al³⁺ Y^(II)S²⁻, Se²⁻ with at least 0.1% in weight of the oxide (M₂O₃) of the M^(III) which is/are present in M^(I)M^(III)Y^(II) ₂, and with at least 0.2% in weight of the oxide, of Y^(II), which is/are present in M^(I)M^(III)Y^(II) ₂, as well as usual refining media if necessary in usual quantities. with the process steps glass batch preparation, melting of the glass, cooling, warming up, whereby 0.1-4% in weight ZnS and/or ZnSe are added to the glass batch.
 10. Use of a glass according to claim 1 or a glass manufactured in the procedure according to claim 9 as optical square edge filter.
 11. Optical square edge filter consisting of a glass according to claim
 1. 12. Use of a glass manufactured by the process of claim 9 as an optical square edge filter.
 13. Optical square edge filter consisting essentially of a glass manufactured by the process of claim
 9. 14. Optical colored glass according to claim 1, characterized by the fact that it contains between 0.1 and 0.5% in weight CuIn(Se_(1−x)S_(x))₂.
 15. Optical colored glass according to claim 2, characterized by the fact that it contains between 0.1 and 0.5% in weight CuIn(Se_(1−x)S_(x))₂.
 16. Optical colored glass according to claim 3 with an edge wavelength λC between 400 nm and 1200 nm.
 17. Optical colored glass according to claim 4 with an edge wavelength λC between 400 nm and 1200 nm.
 18. Optical colored glass according to claim 1 with an edge wavelength λC between 360 nm and 1200 nm.
 19. Optical colored glass according to claim 4 with an edge wavelength λC between 360 nm and 1200 nm.
 20. Optical colored glass according to claim 3 with an edge wavelength λC between 360 nm and 1200 nm. 